Merocyanine dyes containing an aminomethenyl group



United States Patent 0 MEROCYANINE DYES CONTAINING AN AMINOMETHENYL GROUP Edward B. Knott, Harrow,

Kodak Company, New Jersey England, assignor to Eastman Rochester, N. Y., a corporation of No Drawing. Application September 2, 1953, Serial No. 378,167

11 Claims. (Cl. MiG-240.1)

This invention relates to merocyanine dyes, and more particularly, it relates to merocyanine dyes containing an aminomethenyl group and to methods for preparing them.

Merocyanine dyes containing an acid substituent have been previously described. See, for example, Brooker and White, U. S. Patent 2,526,632, issued October 24,

wherein R and R each represent a hydrogen atom, an alkyl group (e. g. methyl, ethyl, n-propyl, isopropyl, nbutyl, isobutyl, carboxymethyl, carbomethoxymethyl, flhydroxyethyl, benzyl, allyl, etc.), acyl (e. g. acetyl, propionyl, butyryl, benzoyl, etc.), aryl (e. g. phenyl, 0-, mand p-tolyl, etc.), cycloalkyl (e. g. cyclobutyl, cyclopentyl, cyclohexyl, etc.) or R and R1 together can represent the non-metallic atoms necessary to complete a heterocyclic ring (e. g. piperidyl, morpholinyl, etc.), R2 represents a hydrogen atom or an alkyl group (e. g. methyl, ethyl, etc.), methyl, ethyl, carbethoxymethyl, ally], benzyl, etc.), R4 represents a hydrogen atom, an alkyl group (e. g. methyl, ethyl, etc.), or an alkoxyl group (e. g. methoxyl, ethoxyl, etc.), It represents a positive integer of from 1 to 2, and

Q represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing from 5 to 6 atoms in the heterocyclic ring, such as those selected from the group consisting of those of the thiazolone series, for example: those of the 2,4(3,5)-thiazoledione series, such as 2,4(3,5)-thiazoledione, 3-alkyl-2,4(3,5)-thiazolediones (e. g. 3-ethyl-2,4(3,5)-thiazoledione, etc.), 3-phenyl- 2,4( 3,5 -thiazoledione, 3-a-naphthyl-2,4( 3,5 -thiazoledione, etc., those of the 2-thi0-2,4(3,5)-thiazoledione (rhodanine) series, such as 3-alkyl-2-thio-2,4(3,5)-thiazolediones (S-alkylrhodanines) (e. g. 3-ethyl-2-thio-2,4(3,5)- thiazoledione (or 3-ethylrhodanine), 3-phenyl-2-thio- 2,4(3,5)-thiazo1edione (Ii-phenylrhodanine), 3-anaph thyl-2-thio-2,4 3,5 -thiazoledione (3-a-naphthylrhodanine), 3-( l-benzothiazyl)-2-thio-2,4( 3,5 )-thiazo1edione (3-(l-benzothiazyl) rhodanine), etc., those of the 2-thio- 2,5(3,4)-thiazoledione series, such as 3-alkyl (e. g. 3- methyl, 3-ethyl, etc.)-2-thio-2,5(3,4)-thiazolediones, etc.,

R represents an alkyl group (e. g.

Fat-enter July 19, I955 those of the 2-alkylmercapto-4(5)-thiazolone series, such as 2-ethylmercapto-4(5)-thiazolone, etc., those of the thinzolidone series, such as 4-thiazolidone or its S-alkyl (e. g. ethyl, etc.), 3-phenyl or 3'a-naphthyl derivatives, those of the 2-alltylphenylamino-4(5)-thiazolone series (e. g. 2-ethylphenylamino-4(5)-thiazolone, etc.), those of the 2-diphenylamino-4(5)-thia2olone series; those of the 5(4)thiazolone series, such as 2-ethylthio-5(4)-thiazolone, 2-ben2ylthio-5(4)-thiazolone, etc., those of the oxazolone series, for example: those of the 2-thio- 2,4(3,5)-oxazoledione series, such as 3-alkyl-2-thio- 2,4(3,5)-oxa2olediones (e. g. 3-ethyl-2-thio-2,4(3,5)-oxazoledione, etc.), those of the 2-imino-2,4(3,5)-oxazolone (pseudohydantoin) series, ctc.; those of the 5(4)-oxazolone series, such as 2-phenyl-5(4)-oxazolone, Z-ethyl- 5(4)-oxazolone, etc., those of the 5(4)-isoxazolone se ries, such as 3-phenyl-5(4)-isoxazolone, etc., those of the imidazolone series, for example: those of the 2,4(3,5)- imidazoledione series, such as 2,4(3,5)-imidazoledione (hydantoin) or its 3-alkyl (e. g. ethyl, etc.), 3-phenyl or 3-iz-naphthyl derivatives as well as its 1,3-dialkyl (e. g. 1,3-diethyl, etc.), l-alkyl-3-phenyl (e. g. 1-ethyl-3-phenyl, etc.), l-alkyl-S-naphthyl (e. g. l-ethyl-3-a-naphthyl, etc.), 1,3-dipheny1, etc. derivatives, those of the 2-thio-2,4(3,5)- imidazoledione series, such as 2-thio-2,4(3,5)-imidazoledione (Z-thiohydantoin) or its 3-alkyl (e. g. S-ethyl, etc.), 3-phenyl or 3-a-naphthyl derivatives as well as its 1,3- dialkyl (e. g. 1,3-diethyl, etc.), 1-alkyl-3-phenyl (e. g. lethy1-3-phenyl, etc.), l-alkyl-B-naphthyl (e. g. 1-ethyl-3- a-naphthyl), 1,3-diphenyl, etc. derivatives, those of the Z-aIkyImercapto-S(4)-irnidazolone series, such as 2-npropyln1ercapto-5(4)-imidazolone; those of the thionaphthenone series, such as 2(l)-thionaphthenone or 1(2)- thionaphthenone; those of the pyrazolone series, such as pyrazolone or its l-alkyl (e. g. methyl, ethyl, etc.), 1- phenyl, l-naphthyl (e. g. l-a-naphthyl), 3-alkyl (e. g. methyl, ethyl, etc.), 3-phenyl, B-naphthyl (3-a-naphthyl), l-alkyl-3-phenyl (e. g. l-methyl-3-phenyl, etc.), 3-alkyll-phenyl (e. g. 3-methyll-phenyl, etc.), 1,3-dialkyl (e. g. 1,3-dimethyl, etc.), 1,3-diphenyl, etc. derivatives; those of the oxindole series, such as 2,3-dihydro-3-ketoindole, and like five-membered heteroeyclic nuclei; those of the 2,4,6 triketohexahydro pyrimidine series, for example, 2,4,6-triketohexahydropyrimidine (barbituric acid), 2- thio-2,4,6-triketohexahydropyrirnidine (Z-thiobarbituric acid) as well as their l-alkyl (e. g. l-ethyl, etc.), or 1,3- dialkyl (1,3-diethyl, etc.) derivatives; those of the 3,4- dihydro-2(1)-quinolone series, such as 3,4-dihydro2(l)- quinolone (dihydrocarbostyril); those of the 3,4-dihydro- 2(l)-quinoxalone series, such as 3,4-dihydro-2(l)quin oxalone (oxydihydroquinoxaline), etc.; those of the 3- phenomorpholone (1,4,3-benzoxazine-3(4) one or beamp-morpholone) series, such as 3-phenomorpholone, etc.; those of the 1,4,2-benzothiazine-3(4)-one (ketodihydrobenzoparathiazine) series, such as ketodihydrobenzoparathiazine, etc., and like six-membered heterocyclic nuclei.

In accordance with my invention, I provide the dyes represented by Formula I above wherein n is l (i. e. simple merocyanine dyes) by condensing together a compound selected from those represented by the following general formula:

II o X wherein R, R1, R2 and R3 each have the values given above, R5 represents an alkyl group (e. g. methyl, ethyl, etc.) or an aryl group (e. g. phenyl, 0-, mand p-tolyl, etc.), and X represents an anion (e. g. chloride, bromide, p-toluenesulfonate, benzene sulfonate, methyl sulfate,

with a compound selected from those reprefollowing general formula:

wherein R4 and Q each have the values given above, with a compound selected from those represented by Formula II above.

The condensations of the compounds of Formula II with those of Formula Ill or 1V can be carried out in the presence of a basic condensing agent, such as the trialkylamines (e. g. trialkylamine, tri-n-butylamine, tri-npropylamine, triisobutylamine, (e. g. N-methylpiperidine, N-ethylpiperidine, etc.), N,N- dialkylanilines (e. g. N,N-dimethylaniline, N,N-diethylaniline, etc.) etc. The condensations can advantageously be carried out in the presence of an inert solvent, such as pyridine. lower aliphatic alcohols (e. g. ethanol, n-propanol. n-butanol, etc.) 1,4-dioxane, etc. Heat accelerates the condensations and temperatures varying from room temperature to the reflux temperature of the reaction mixture can be used.

The intermediates represented by Formula 11 above can advantageously be prepared by heating together a compound selected from those represented by the following general formula:

wherein R. R1, R2 and R each have the values given above with an alkyl salt selected from those represented by the following general formula:

wherein R5 has the values given above. The intermediates of Formula V can advantageously be prepared by condensing together a compound selected from those represented by the following general formula:

wherein R2 and R3 each have the values given above, and R represents an alkyl group (e. g. methyl, ethyl, etc.) with a nitrogen compound selected from those represented by the following general formula:

VIII

R-NH wherein R and R1 each have the values given above. Examples 1-15 and 60 below describe the preparation of a number of intermediates coming within the scope of Formula V11 above. Examples 1630, 52, 53, 54 and 61 below describe the preparation of a number of intermediates coming within the scope of V above.

The preparation of a number of intermediates coming within the scope of iv above has been described in Collins et a1. British Patent 528,803 ([lford), accepted November 7, 1940. This patent describes only intermediates of Formula 1V above wherein R4 is a hydrogen atom or an alkyl group. Intermediates of Formula 1V wherein R4 is an alltoxyl group have been previously described in Kendall et al. British Patent 544.647 (llford), accepted April 22. 1942. The preparation of a number of intermediates etc.), N-alkylpiperidines coming within the scope of IV has also been described in my copending application Serial No. 309,743, filed September 15, 1952. Also, it will be noted that Formulas IV and VII are identical when R2 represents a methyl group and R4 represents an alkoxyl group. The preparation of the intermediates of VII wherein R2 represents a hydrogen atom has been described in Kendall et a1. British Patent 633,736 (Ilford), accepted December 19, 1949.

The dyes of Formula I above wherein R and R1 represent an acyl group can advantageously be prepared by condensing a mero-cyanine dye selected from those represented by I above wherein R or R1 (or both) represent a hydrogen atom with a carboxylic anhydride (e. g. acetic, propionic, butyric, isobutyric, benzoic, etc., anhydrides).

The following examples will serve to illustrate more fully the manner whereby I practice my invention.

Example I .3-crrrbethoxymethyl-S-l -etlz0xyethylidene 2-thz'othiaz0lid-4-0ne 3-carbethoxymethylrhodanine (4.38 g.), ethyl orthoacetate (6.0 cc.), and acetic anhydride (25.0 cc.) were refluxed for one hour and the solvents removed. There were thus obtained 4.9 g. of residual solid (yield=% of theory) as silky, bufl needles melting at C. on recrystallization from ligroin.

Example 2..i-curbeth0xymethyl-5-eth0xymethylene-2- (hi0thinz0lid-4-0nc Example 3.3-carbethoxymethyl-5-1-etlz0.rypr0pylidene- 2-tlzi0thiaz0lid-4-0ne 3-carboxymethyl-2-thiothiazolid-4-one (30 g.), ethyl orthopropionate (50 cc.) and acetic anhydride (100 cc.) were refluxed for 1 hour and the solvents removed under reduced pressure. The residual oil was extracted with boiling ligroin until no furtherer yellow color appeared in the solvent. Concentration to 100 cc. followed by chilling gave brown crystals (7.2 g.) which formed brown leaflets, M. P. 98 C., from isopropanol.

Example 4.-5-etl1oxymethylene-3-phenyl-Z-thi0tlziazolid- 4-0ne 3-phenyl-2-thiothiazolid-4-one (20.7 g), ethyl orthoformate (30 cc.) and acetic anhydride (100 cc.) were refluxed for 1 hour in an oil bath at C. Removal of solvents under reduced pressure gave a red solid which was boiled up with ethanol (100 cc.) to remove the red dye. The buff powder was washed with acetone and it (14.0 g.) formed flat cream needles, M. P. l5l C., from ethanol.

Example 5.5-1 '-ethoxyethylidene-3-phenyl-2th iothiazolid4-one Obtained similarly from 3-phenyl-2-thiothiazolid-4-one and ethyl orthoacetate in 93.5% yield, formed orange needles, M. P. 164--l66 C., from methanol.

Example 6.-5]-eth0xypr0pylidene-3-phenyl-Z-thiothiaz0lid-4-one Obtained similarly using ethyl orthopropionate it formed yellow plates, M. P. l82 C.

Example 7.3allyl-5-etlmxymethylene-2-tlzi0thiaz0lld-4-one 3-allyl-2-thiothiazolidl-ohe (7.0 g.), ethyl orthoformare (25 cc.) and acetic anhydride (50 cc.) were refluxed for 5 hours and the solvents removed. The purple tar was dissolved in isopropanol (25 cc.), chilled and scratched. The crystals were collected and washed with ice-cold isopropanol to remove oxonol dye. It (6.4 g.) formed glassy, garnet needles, M. F. 5455 C., from cyclohexane.

Example 8.3-allyl-5-1-ethoxyethylidene-2-thi0- thiazolid- -one Same as for Example 7 using ethyl orthoacetate (25 cc.); it (8.7 g.) formed large brown plates, M. P. 6354 C., from light petroleum (B. P. 6080 C.).

Example 9.3-allyl-5-1'-eth0xypr0pylidene-Z-thiothiazlid-4-one Same as for Example 7 using ethyl orthopropionate; it (6.0 g.) formed yellow needles, M. P. 6263 C., from isopropanol.

Example 10.-3-benzy[-5-eth0xymctlzylene-Z-lhiolhiaz0lid-4-0ne 3-benzyl-2-thiothiazolid-4-one(5.5 g.), ethyl orthoforrnate (25 cc.) and acetic anhydride (50 cc.) were refluxed for hours and the solvents removed. The solid (5.2 g.) formed pink needles, M. P. 87 C., from isopropanol.

Example ]1.3-benzyl-5- I -ethoxyethylidene-Z-thioth iaz0lid-4-one Proceeding as in Example but using ethyl orthoacetate instead of ethyl orthoformate the product (4.2 g.) was obtained as flat, straw colored needles, M. P. 109 C., from isopropanol.

Example I 2 .-3-cycl0h exyl-5-ethoxymethylene-Z-th i0- thiaz0lid-4-0ne 3-cyclohexyl-2-thiothiazolid-4-one (11.2 g.), orthoformate cc.) and acetic anhydride cc.) were refluxed for 2% hours and the solvents removed. The product (7.1 g.) was obtained as pale yellow needles, M. P. 139-140 (3., from isopropanol.

Example I 3.3 -cycl0hexyl-5 -etlioxyethylidene-Z-thi0- thiaz0lid-4-0ne 3-cyclohexyl-Z-thiothiazolid-4-one (56 g.), ethyl orthoacetate cc.) and acetic anhydride (500 cc.) were refluxed for 6 hours and the solvent removed. The product (44.0 g.) formed pale orange flakes, M. P. 125-126" C., from isopropanol.

Example ]4.3-allyl-5-I'-methoxyethylidene-Z-thi0- tl1z'azolid-4-0ne 3-allyl-2-thiothiazolid-4-one(8.7 g.), methyl orthoacetate (10.5 cc.) and acetic anhydride (50 cc.) were refluxed for 5 hours. Further orthoacetate (10.5 cc.) and anhydride (50 cc.) were added and refluxed a further 6 hours. Removal of solvent left an oil which crystallized on standing. From isopropanol (thrice), it (5.1 g.) formed brown needles, M. P. 83-84 C.

Example 15.3-carbetlz0xymethyl-5-1'-methoxyethylidene-Z-thiothiazolid-4-ane 3-carbethoxymethyl-2-thiothiazolid-4-one (1 1.0 g. methyl orthoacetate (21 cc.) and acetic anhydride (100 cc.) were refluxed for 1 hour and the solvents removed. The solid (13.4 g.) formed straw-colored needles, M. P. 113-114.5 C., from isopropanol.

Example I 6 .5 '-anilinoethylidene-3-carbethoxymethyl-Z-thiothiazolid-4-0ne 3 carbethoxyrnethyl 5 l ethoxyethylidene 2- thiothiazolid-4-one (2.9 g.), aniline (0.92 cc.), and ethanol (10 cc.) were refluxed for 30 minutes, cooled,

ethyl I and the crystals (2.65 g.) recrystallized from ethanol cc.). It formed golden laths, M. P. 173175 C.

Example ]7.-3-carbethoxymethyl-5-piperid-1'-ylmethylene-Z-thiothiazolid-4-0ne 3 4 c arbethoxymethyl 5 ethoxyrnethylene 2 thio- 1hra2ol1d-4-one )1.4 g.), ethanol (10 cc.) and piperidine (0.5 cc.) reacted at room temperature. The mixture was then heated for 2 minutes on the steam bath, cooled and the crystals collected. From benzene it (1.2 g.) formed fine, pale yellow needles, M. P. l46-l47 C. Example l8.--3carbezhoxymethyl-5-morph0lin-3-ylme- 3 carbethoxymethyl 5 ethoxymethylene 2 thioth1azolid-4-one (1.4 g.), benzylamine (0.55 cc.) and ethanol (10 cc.) were refluxed for /2 hour. The solutron was chilled overnight and the yellow needles (1.05 g.) recrystallized from ethanol. It formed yellow needles M. P. 109-110 C.

l Example 2]. 3 allyl 5 ethylaminomethylene 2- zit) 3 allyl 5 ethoxymethylene 2 thiothiazolid 4- one (4.6 g.) and ethanol (15 cc.) were shaken to dissolve and ethylamine (5 cc. 33% alcoholic solution) was added. Heat was evolved and the liquid set solid with crystals. These (4.0 g.) were collected after chilling and washed with a little ice-cold ethanol. It formed soft, pale yellow threads, M. P. 132 C., from ethanol.

Example 22. 3 ally] 5 diethylaminomethylene 2- lhiothiaz0lid-4-0ne O=C-NCH2UH=CH2 LaHiNUH=u Cilia S 3 allyl ethoxymethylene 2 thiothiazolid 4- one (2.3 g), ethanol cc.) and diethylamine (1.05 cc.) were heated for 2 minutes on the steam bat The crystals (1.7 g.) were collected after chilling and formed flat, yellow needles, M. P. 74 C., from isopropanol.

Example 23. 3 allyl 5 morpholin 3' ylmethylene-2-thi0thiaz0lid-4-one O=C N--CH1CH=CH2 3-ally1-5-ethoxymethylene-2-thiothiazolid-4-one (2.3 g.), ethanol (10 cc.) and morpholine (0.95 cc.) were mixed. The reaction product separated rapidly and the reaction was completed by heating for 2 minutes on the steam bath. It (2.3 g.) formed flat, yellow needles, M. P. 180 C., from benzene.

Example 24. 3marbethoxymethyl-S-cyclohmyluminomethylene-Z-thiothiazolid-4-0ne 3 carbethoxymethyl 5 thiazolid-4-one (2.75 g.), hexylamine (1.25 cc.) were 5 minutes, chilled and the ethoxymethylene 2 thioethanol (10 cc.) and cycle heated on the steam bath for crystals (2.3 g.) collected.

It formed yellow tablets, M. P. 133-134 C., from isopropanol. Example 25. 3-11llyl-5-n-0ctylamin0methylene-2-thi0- O:C-N-CH:CH=CH1 (")CgHrr-NH-LHzz =S 3 allyl-S-ethoxymethylene-2-thiothiazolid-4-one (2.3 g.), ethanol (10 cc.) and n-octylamine (1.3 g.) were heated on the steam bath for 5 minutes. The whole solidified on chilling. it (2.85 g.) formed pale yellow threads, M. P. 98l00 C., from ethanol.

Example 28. 3 carbethorymelhyl 5 dicyclohexylaminomethylene-Z-thiothiaz0lid-4-one l O=C--NCH2C*0C1H5 3 carbethoxymethyl 5 ethoxymethylene 2 thiothiazolid-4-one (3.5 g.) dicyclohexylamine (2.4 cc.) and ethanol cc.) were refluxed for minutes. The solid (3.8 g.) formed pale yellow tablets, M. P. 159 C., from ethanol.

Example 29.3-carbethoxymethyl-5-I'-ethylamin0ethylidene-Z-thi0thiaz0lid-4-0ne 3 carhethoxyrnethyl 5 1- ethoxyethylidene 2 thiothiazolid-4- one (2.9 g.), ethanol (10 cc.) and ethylamine (33% alcoholic, 2.5 cc.) were mixed. A solid separated and the whole was heated for 2 minutes on a steam bath. it (2.9 g.) formed soft, creamy plates, M. P. 121 C., from ethanol.

Example 30.-3-allyl-5-l '-etlzylaminoerhylidene- 2-thr'0thiazolid-4-one 3-a1lyl-5-1-ethoxyethylidene-Z-thiothiazolid-4-one (2.45 5.); ethanol (10 cc.) and ethylamine (33% alcoholic, 2.5 cc.) were mixed then heated for 5 minutes on a steam bath. The substance (2.25 g.) which crystallized slowly on chilling formed straw-colored flakes, M. P. C., from ethanol.

Example 26. 2,5-diaza-1,6-di-(3-carbeth0xymethy1-4- kem-Z-thiothiazolidin- -ylidene)hexane 3 carbethoxymethyl 5 ethoxymethylene 2 thiothiazolid-4-one (5.5 g.) was dissolved in boiling ethanol (25 cc.) and ethylenediamine hydrate (0.81 cc.) added, then refluxed 15 minutes. A thick oil separated on chilling. It slowly crystallized (3.6 g.), was dissolved in boiling ethanol (150 cc.) and obtained as soft, pale yellow needle aggregate, M. P. 145 C.

Example 27. 3-carbe1hoxymethyl-S-dibenzylaminomethylene-2-thiothiaz0Iid-4-0ne 3-carbethoxymethyl 5 -ethoxymethylene thiothiazolid-4-one (5.5 g.), dibenzylamine (3.85 cc.) and ethanol were refluxed for 30 minutes. Chilling gave a tar which slowly crystallized. From ethanol it (8.0 g.) formed soft, slender yellow needles, M. P. 103l04 C.

Example 3].-3-cm'bctlwxymcthyl-Z-(3-carbeth0xymethy! 4 [(PTO 2 illlOl'llllIIfOlldlH 5 ylidene)- 5-piperirl- 1'-ylmeflzjrlmictl:[undid-4mm 10 Example 32.3-carbeth0xymetlzyl-2-(3-carboxymethyl-4- Example 36 keza 2 thiothiazolidin 5 ylidene) 5 morpholin- CH2CH=CH2 O CHl} H O (n)CuHi7NH-CH=L J 3% :5 O- -C-Ii 0 6 2 N-CH OH \s/ \S/ g 1 2 Intermediate 1V From Example 25. S Intermediate III 3-allyl-2-thiothiazolid-4-one.

s s 10 Yield 62%. The intermediate of Example 18 (0.95 g.) and dimeth- Appliarance ';f ylsulphate (0.3 cc.) were fused at 125 C. for 30 minutes. m i 3-carboxymethyl-Z-thiothiazolid-4-0ne (0.6 g.), ethanol It sensitized a photographic silver chlorobromtde emul- 10 and triethylamgne 0 Wsre added and h sionand a photographic silver iodobromide emulsion with whole heated on a steam bath for 10 minutes. After 1.; maXlma at 490 mu. cooling the clear solution was acidified with dilute acetic Ex m 18 37 acid. The crystals (1.1 g.) which separated overnight a p formed yellow threads, M. P. 251 C. (dee) from meth- CHCH=CH anol. It sensitized a silver chlorohromide emulsion O=C l\ =C- NCHzUH=CHi powerfully with a peak at 530 mu at 0.5 g. per 1000 g. :3 equivalent of silver nitrate. Example 33.-.?-a1lyl-2-(Z-ethylth1'o-5-ket0thiazolin-4-yl- {m mm 1V F Example 2 izlene)-5-n-octylanzinomethylerte tlziaz0lirl-4-0ne mt m di III 3-ally] 2-1hi thiaz ]id-4- ne CHZCH=GH2 Yield Appearance Orange flakes. =C- C 1 i Z MP 177C. (I1)CgH 7NHCH -'C 2 i SCzH,-,

\ Example 38 CH CH=CH The intermediate of Example (0.8 g.) and methyl 2 2 p-toluenesulphonate (0.5 g.) were fused at 140 C. for 0= 0:6 N CHECH=CH 2 hours. N-dithiocarhethoxyglycine (1.0 g.), and acetic K 5 N-CH: (i=0 =8 anhydride (20 cc.) were heated on a steam bath for 1 hour and the solvents removed. The residual oil and W Iii t IV F the quaternary salt were mixed with ethanol (10 cc.) and l e m P triethylamine (1 cc.) and heated for 5 minutes 011 a steam Sig late gg bath. The yellow needles (0.3 g.) obtained on chilling 0 Z" formed soft, yellow threads, M. P. 156 C. from ethanol. ppgarance c needles M. P 244 C. Example 34.-3 carbetlzoxymelhyl 2 (3 ethyl 4 40 E keto 2 thiooxazolidin 5 ylidene) 5 morphollnxample 39 3'-ylmethylenethiaz0lid-4-0ne CHCH=CH 0 O=(|7N 0=C 1Iw-omc1i=- CH, mild-002B. CEHPNMSHQK :8

C H S \Q 0=o-N 0=C-NCQH5 5 L fi N CH 5 A A 1 q Intermediate IV From Example 22.

a Intermediate III 3-allyl-2-thi0thiazolid-4-one. s o Yield 47%. The intermediate of Example 18 (1.0 g.) and methyl e s threads p-toluenesulphonate (0.6 g.) were fused at 130 C. for 1 hour. 3-ethyl-2-thiooxa2olid--4-one (0.5 g.), ethanol Example 40 (10 cc.) and triethylamine (0.5 cc.) were added and CH2CH=CH2 heated on a steam bath for 10 minutes. The yellow grains (0.5 g.) formed yellow needles, M. P. 155457 C., (g from isopropanol. CZH5 NH-C= a In a manner similar to that illustrated above, the fol- H3 lowing dyes of Examples 35 to 44 were prepared.

I Intermediate IV From Example 30. Recrystallizations were made from benzene-ethanol. m] Intermediate 1H 3-a1lyl 2 thI-0thiamh-d443m Example 35 Yleld Appearance Rust crystals. M. P 210 C.

i CH OC H 2 2 5 Example 41 0=o- N 0=C N-oHloH=cH, I l I CH2CH=CH2 o s NCH= =s I It 0=C-N 0=0- N-cHlc-oolm S 6 s N-0H=h d=s Intermediate IV From Example 18. l t ed t Ill 3- 1l1-2-thioth'a olid-4-one.

la 6 70 1 2 Intermediate IV From Example 23. g gg yeuw needles Intermediate III Q-CHTIJCKllOXYmGIltyLZ-IlliOtilh M P 0 C I azolid-4-one.

Yield 30%. It sensitized a gelatino-silver chlorobromide emulsion with Appearance Violet crystals.

a maximum at 510 mu. M. P 224 C.

Example 42 CH: S 8

Intermediate IV From Example 29. Intermediate Ill Same as Example 41. Yield 70%.

Appearance Orange threads.

M. P 158 C.

Example 43 From Example 27. Same as Example 41.

Intermediate 1V Intermediate Ill Yield 28%.

Appearance Yellow threads.

M. P 185 C.

Example 44 From Example 28. Same as Example 41 Intermediate IV intermediate III The intermediate of Example 26 (1.3 g.) and methyl p-toluenesulfonate (1.0 g.) were fused at 120 C. for 30 minutes. 3-carbethoxymethyl-Z-thiothiazolid-4-one (1.1 g.), ethanol (20 cc.) and triethylamine (0.8 cc.) were added and the whole heated for 15 minutes on the steam bath. The dye oiled out, then crystallized on chilling. It (1.3 g.) formed orange crystals, M. P. 232 C., from pyridine-ethanol.

Example 46.-acetethylamidomethylene-3-ally[-2-(3-allyl-4-ket0-2-thiothiazolidin-5-ylidene) thiazolid-4-0ne The dye of Example 37 (1.0 g.) and acetic anhydride (25 cc.) were refluxed for 3 hours and the solvent removed. The residual crystalline cake formed slender orange-brown needles, M. P. 160-161 C., from ethanol.

1 2 Example 47.-3-carbezh0xymethyl-2-(3-carbethoxymethyl-4-keto2-thiothiazolidine-S-ylidene ethylidene)-5-piperid-I -ylmethylenethiazolid-40ne The intermediate of Example 17 (1.2 g.) and methyl p-toluenesulphonate (0.75 g.) were fused at 125 C. for 1% hours. 3-earbethoxymetl1yl-5-ethylidene-2-thiothiazolid-4-one (0.95 g.), ethanol cc.) and triethylamine 0.6 cc.) were added and heated on a steam bath for 3 minutes. The dye (0.65 g.) which crystallized from the hot solution formed rust-red threads, M. P. 196 C. from benzene. lt sensitized a silver chlorobromide emulsion with a peak at 630 mu and a silver iodobromide emulsion with a peak at 620 mu.

Example 48.3 carbeth0xymethyl-2-[2-(3 cnrbethoxymethyl-4-keto-2-thiothiazolidirr 5 ylidene)prop-1-ylidene] -5-piperid-2-ylmethylenethiazolid-4-one UHa S The intermediate of Example 17 0.95 g.) and methyl p-toluenesulphonate (0.6 g.) were fused at 125 C. for 1 hour. 3 carbethoxyrnethyl 5 prop-1'-ylidene-2-thi0- thiazolid-4-one (0.8 g.), ethanol (10 cc.) and triethylamine (0.5 cc.) were added and refluxed for 5 minutes. The dye (0.5 g.) collected, after chilling, formed soft, pink needles, M. P. 200 C., from benzene-ethanol. It sensitized a silver chlorobromide emulsion strongly with a peak at 620 mu and a silver iodobromide emulsion with a peak at 570-630 mu.

{5 Example 49.3 carbeth0xymethyl2-[2-(3 carbethoxymethyl-4-ket0-2-thi0thlaZ0lidin-5-ylidene) Z-melhoxyethylidenel -5piperid-I'-ylmethylenethiaz0lid-4-one The intermediate of Example 17 (0.95 g.) and methyl p-toluenesulphonate (0.6 g.) were fused at 25 C. for l hour. Substance of Example 15 (0.85 g.), ethanol (10 cc.) and triethylamine (0.5 cc.) were added and refluxed for 5 minutes. The dye (0.6 g.) collected after chilling formed soft, red needles, M. P. 129 C., from benzeneethanol. It sensitized a silver chlorobromide emulsion strongly with a peak at 600 mu.

Example 50.3ally1-2-[2-(3-aI1'yl-4-ket0-2-thi0thlazolidin-5-ylidene) prop-Z-ylidene] -5-n-0ctylaminomelhylenethiazolid-4-0ne The intermediate of Example 25 (1.55 g.) and methyl p-toluenesulphonate (0.95 g.) were fused at 140 C. for 2 hours. 3 -allyl-5-prop-2'-ylidene-2-thiothiazolid-4-one (1.1 g.), ethanol (10 cc.) and triethylamine (0.8 cc.) were added and the whole refluxed for 5 minutes. After concentration and chilling the dye (0.8 g.) formed green red threads, M. P. 138 C., from methanol.

Example 51 .3-allyl-2-[2-(3-allyl-4-kezo-2-thiotlu'azolidin-5-ylidene -2-eth0xy ethylia'ene -5n-0Ctylrrm inometh ylenethiazlid-4-one Example 52-3 allyl--1-ethylamin0pr0pylidene-2-lhi0- thiazolid-4-one O=C NCH2CH=UH: C2H5-NH-('J= CzH5 S Compound of Example 9 (2.6 g.), ethanol (5 cc.) and 33% alcoholic ethylamine (2.5 cc.) were mixed and chilled for several weeks. The crystals (1.8 g.) formed orange flakes, M. P. 49-51 C., from isopropanol.

Example 53.3 ally! 5 aminomethylene-Z-thiothiazolid-4-one o=c N-cmcn=cm NH2CH=(B :S

Compound of Example 7 (2.3 g.), ethanol (10 cc.) and 0.880 ammonia (5 cc.) were brought to boiling point on the steam bath. The solution was cooled and water (5 cc.) added. Crystallization commenced and water (10 cc.) was then added and the whole chilled overnight. The solid (1.8 g., 90%) formed orange-brown needles,

Compound of Example 7 (4.6 g.) was added to a solution of glycine (1.5 g.) and potassium hydroxide (1.15 g.) in water (5 cc.) and ethanol (10 cc.). The Whole was heated for 5 minutes on the steam bath, cooled and acidified with dilute acetic acid. The required compound crystalilzed slowly on dilution with water. It (4.65 g., 90%) formed mustard yellow needles, M. P. 195-196 C., from aqueous ethanol.

Example 55.3 allyl 2 [2 (ethoxy 2 (2 ethyl- !lzio 5 kelotlziazolin 4 ylidene)ethylidene] 5- morpholln-3'-ylmethylenethiaz0lid-4-one Compound of Example 23 (2.7 g.) and methyl p-toiuenesulphonate (2.0 g.) were fused at 130 C. for 2 hours. 5 1 ethoxyethylidene 2 ethylthiothiazol 5 one (2.3 g.), ethanol (10 cc.) and triethylamine (1.5 cc.) were added and refluxed for 5 minutes. The dye 1.1 g., 24%) collected after chilling formed soft magenta threads, M. P. 176 C., from ethanol.

Example 56.3 allyl 2 (3 allyl 4 keto 2 thiatlziazollclin 5 ylidene) 5 carboxymethylaminomethylenethiazolid-l-one Compound Example 54 (1.3 g.) and methyl p-toluenesulphonate (0.95 g.) were fused at 130 C. for 1 hour. 3-allylrhodanine (0.9 g.), ethanol (10 cc.) and triethylamine (1.5 cc.) were added and the whole refluxed for 5 minutes. On acidifying with dilute acetic acid the dye crystallized. It (1.3 g., formed brown prisms, M. P. 224-226 C., from ethanol.

Example 57.3 allyl 2 (2 diphenylamino 4 ketothiazolin 5 yliclene) 5 morpholin 3 lymethylenethiaz0lid-4-one Compound of Example 23 (1.35 g.) and methyl p-toluenesulphonate (1.0 g.) were fused at 130 C. for 2 hours. 2-diphenylaminothiazol-4-one (1.35 g.), pyridine (10 cc.) and triethylamine (0.8 cc.) were added and heated on the steam bath for 15 minutes. Ethanol (30 cc.) was added and the crystals (1.2 g., 47.5%) collected after chilling. The dye formed an orange-brown crystalline powder, M. P. 290 C. (dec.), from benzene-ethanol.

Example 58.3 allyl 2 (3 allyl 4 keto 2 thi0- thiazolid 5 ylidene) 5 (3 ally! 4 keto 5 nnctylaminomethylenethiazolidin 2 ylidene)lhiazolid- 4-one CHzCH=CHg CH3CH=CH2 =C N O=1\N O=C--N--CH3OH=CH| (n)C H NH QH= 1:2: =3

M. P. l04-109 C., from aqueous ethanol. Dye of Example 36 1.5 g.) and methyl p-toluenesul- Example 54.3 allyl 5 carboxymethylaminomethylene-Z-thiothiazolid-4-0ne O=C N-CHzCH=CH2 0 130-15 om-NH-cn=d 0:5

phonate (0.65

g.) were fused at C. for 1 hour. 3-allylrhodanine (0.6 g.), ethanol (15 cc.) and triethylamine (0.5 cc.) were added and refluxed for 5 minutes. The dye (1.25 g., 63.5%) was collected after chilling and formed soft red needles, M. P. 199-201 C., from benzeneethanol.

Example 59.-3 allyl 2 [3 allyl2- (3 -allyl-4- lidin 5 ylidene] -5 (3 allyl 4 keto 5 n octylaminomethylenethiazolidin-Z-ylidene)thiazlid-4-0ne Dye of Example 58 (0.7 g.) and methyl p-toluenesulphonate (0.5 g.) were fused at 140 C. for 30 minutes. To the solid quaternary salt was added, 3-allylrhodanine (0.25 g.), and ethanol (15 cc.) and the flask warmed gently to dissolve the solids. The addition of triethylamine (0.3 cc.) gave an immediate precipitation of dye. It (0.6 g., 70%) formed a red, crystalline powder, M. P. 263 C., from pyridine.

60.-1'-ethoxyethylidene 3 ethyl 2 thiathiazolidl-one Freshly distilled 3-ethylrhodanine (20 g.), ethyl orthoacetate (50 cc.) and acetic anhydride (100 cc.) were retluxed on a gauze for 4 hours and the solvents removed under reduced pressure. chilling. From isopropanol a yield of 14.6 g. (51%) orange needles, M. F. 80 C., was obtained.

Example Example 61.3 ethyl 5 1' ethylaminoethylidene 2- rhiothiaz0lid-4-one Example 62.--3 ethyl-2-(3ethyl-Z-thiothiazolidin 5- ylidene)-5-1'-ethylamirm ethylidenethiaz0Iid-4-0ne CzHs Compound of Example 61 (1.15 g.) and methyl tolu ene-p-sulphonate (1.0 g.) were fused together at 120 for 1 hour. 3-ethylrhodanine (0.85 g.), ethanol (20 cc.) and triethylamine (0.8 cc.) were added and the whole refluxed for 5 minutes. The dye which separated during this time was collected after chilling and washed with ethanol. It (1.4 g., 78.5%) formed orange needles M. P. 247 C., from benzene.

As shown in a number of the above examples, the new dyes of my invention are useful in spectrally sensitizing photographic silver halide emulsions when incorporated therein. The dyes are especially useful for extending the spectral sensitivity of the customarily employed gelatino silver chloride, gelatino silver chlorobromide, gelatino silver bromide, gelatino silver bromiodidc, and gelatino silver chlorobromiodide developing-out emulsions. In several of the foregoing examples, the point of maximum sensitivity of gelatino silver chlorobromide and/or gelatino silver bromiodide emulsions sensitized with my new dyes is pointed out in connection with the description of the. properties of certain of the dyes. To prepare emulsions sensitized with one or more of my new dyes, it is only necessary to disperse the dye or dyes in the emulsions. The methods of incorporating dyes in emulsions are simple and are known to those skilled in the art. In practice, it is convenient to add the dyes to the emulsions in The residual oil solidified on i the form of a solution in an appropriate solvent. Methanol or acetone has proved satisfactory as a solvent for most of my new dyes. Where the dyes are quite insoluble in methyl alcohol, a mixture of acetone and pyridine is advantageously employed as a solvent. The dyes are advantageously incorporated in the finished, washed emulsions and should be uniformly distributed throughout the emulsions.

The concentration of the dyes in the emulsions can vary widely, e. g. from 5 to 100 mg. per liter of fiowable emulsion. The concentration of the dyes will vary according to the type of emulsion and according to the effect desired. The suitable and most economical concentration for any given emulsion will be apparent to those skilled in the art, upon making the ordinary tests and observations customarily used in the art of emulsion making. To prepare a gelatino-silver-halide emulsion sensitized with one or more of my new dyes, the following procedure is satisfactory:

A quantity of dye is dissolved in methyl alcohol or acetone (or a mixture of acetone and pyridine) and a volume of this solution, which may be diluted with water, containing from 5 to 100 mg. of dye, is slowly added to about 1000 cc. of gelatino'silver-halide emulsion, with stirring. Stirring is continued until the dye is thoroughly dispersed in the emulsion.

With most of my dyes, from to mg. of dye per liter of gelatino-silver-bromide or bromiodide emulsion (containing about 40 g. of silver halide) sufiices to produce the maximum sensitizing effect. With the finer grain emulsions, somewhat larger concentration of dye may be needed to produce the maximum sensitizing effect.

The above statements are only illustrative, as it will be apparent that the dyes can be incorporated in photographic emulsions by any of the other methods customarily employed in the art, e. g. by bathing a plate or film upon which an emulsion is coated in a solution of the dye in an appropriate solvent. However, bathing methods are ordinarily not to be preferred. Emulsions sensi tized with the dyes can be coated on suitable supports, such as glass, cellulose derivative film, resin film or paper in the usual manner.

Tabulated below are sensitizing data obtained from dyes of a number of examples, which examples give an indication of the sensitizing properties or the dyes described. These data supplement those of the above examples. The sensitizing maxima are given in mu.

. Silver chloro- Silver indo- Emmi'lo bromide bromide 33. 430 34 490 400 a 530 s :58. 525 52s as. 53m 530 530 530 41. san s30 Photographic silver halide emulsions, such as those listed above, containing the sensitizing dyes of my invention can also contain such addenda as chemical sensitizers, e. g. sulfur sensitizers (e. g. allyl thiocarbamide, thiourea, allylisothiocyanate, cystine, etc.), various gold compound; (e. g. potassium chloroaurate, auric trichloride, etc.) (see U. S. Patents 2,540,085; 2,597,856 and 2,597,915), various palladium compounds, such as palladium chloride (U. S. 2,540,086), potassium chloropalladate (U. S. 2,598,079), etc., or mixtures of such sensitizers; antifoggants, such as ammonium chloroplatinate (U. S. 2,566,245), ammonium chloroplatinite (U. S. 2,566,263), benzotriazole, nitrobenzimidazole, S-nitroindazole, benzidine, mercaptans, etc. (see MeesThe Theory of the Photographic Process, Macmillan Pub., page 460), or mixtures thereof; hardeners, such as formaldehyde (U. S. 1,763,533), chrome alum (U. S. 1,763,533), glyoxal (U. S. 1,870,354), dibromacrolein (Br. 406,750), etc.; color couplers, such as those described in U. S. Patent 2,423,730, Spence and Carroll U. S. application Ser. No. 771,380, filed August 29, 1947, etc.; or mixtures of such addenda. Dispersing agents for color couplers, such as those set forth in U. S. Patents 2, 322,027 and 2,304,940, can also be employed in the above-described emulsions.

What I claim as my invention and desire secured by Letters Patent of the United States is:

I. A merocyanine dye selected from those represented by the following general formula:

wherein R and R1 each represents a member selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to 8 carbon atoms, an acetyl group, a propiouyl group, a butyryl group, an isobutyryl group and a benzoyl group, a monocyclic aryl group of the benzene series, a cycloalkyl group containing from 4 to 6 atoms in the cycloalkyl ring, and R and R1 together represent the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of piperidine and morpholine, R2 represents a member selected from the group consisting of a hydrogen atom and an alkyl group containing from 1 to 2 carbon atoms, R represents an alkyl group containing from 1 to 4 carbon atoms, R4 represents a member selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to 2 carbon atoms, and an alkoxyl group containing from 1 to 2 carbon atoms, 11 represents a positive integer of from 1 to 2 and Q represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the 2,4(3,5)-thiazoledione series, those of the rhodanine series, those of the 2-thio-2,5(3,4)- thiazoledione series, those of the 2-alkylmercapto-4(5)- thiazolone series, those of the thiazolidone series, those of the 2-alkylphenylamino-4(5)-thiazolone series, those of the 2-diphenylamino-4(5)-thiazolone series, those of the 5 (4)-thiazolone series, those of the 2-thio-2,4(3,5)- oxazoledione series, those of the pseudohydantoin series, those of the 5(4)-oxazolone series, those of the 5 (4)- isoxazolone series, those of 2,4(3,5)-imidazoledione series, those of the 2-thio-2,4(3,5)-imidazoledione series, those of the 2-alkylmercapto-5(4)-imidazolone series, those of the thionaphthenone series, those of the pyrazolone series, those of the oxindole series, those of the 2,4,6-triketohexahydropyrimidine series, those of the 3,4- dihydro-2(1)-quino1one series, those of the 3,4-dihydro- 2(1)-quinoxazolone series, those of the 3-phenomorpholone series, and those of the 1,4,2-benzothiazine-3 (4)- one series.

2. A merocyanine dye selected by the following general formula:

from those represented fill 3. A merocyanine dye selected from those represented by the following general formula:

0 0=(|)NRs ii-s RlNH-CH=C 05-3-11 S N wherein R1, R and R3 each represents an alkyl group. 4. A merocyanine dye selected from those represented by the following general formula:

5. A merocyanine dye selected from those represented by the following general formula:

6 S N-CH=( 3 (J1 (JJ-N(R') wherein R3 represents a lower alkyl group and R represents a monocyclic aryl group of the benzene series.

6. A merocyanine dye selected from those represented by the following general formula:

0=C-NRs CN-R RiNHOH=l =3 each represents a lower alkyl wherein R1, R3, and R group.

7. The merocyanine dye having the following formula:

s 9. The merocyanine dye having the following formula:

CHzfll-OCrHs O=E-Il O=Z-NC:Ha 6 S N-CH: =S L 10. The merocyanine dye having the following formula:

CHgCH=CHa 11. The merocyanine dye having the following formula:

CHrCH=CHI No references cited. 

1. A MEROCYANINE DYE SELECTED FROM THOSE REPRESENTED BY THE FOLLOWING GENERAL FORMULA: 